The present invention generally relates to the field of Raman spectroscopy, and more particularly, to a sensor for detecting chemicals both in gas and liquid environments using surface enhanced Raman spectroscopy whereby any Raman scattering due to excitation of the optical elements of the sensor are minimized.
Raman spectroscopy is an emission technique that involves inelastic scattering of incident laser energy and results in spectral peaks that are frequency shifted from the incident energy. The Raman bands arise from changes in polarizability in a molecule during vibration. As a result, virtually all organic molecules display a characteristic Raman emission. Therefore, a Raman sensor would not be limited to a specific class of molecules as is the case for a laser induced fluorescence (LIF) sensor. Raman spectrometry allows the fingerprinting of species present and is structurally specific. The inherently high resolution of Raman spectra often permits the analysis of several components in a mixture simultaneously.
The advent of inexpensive, portable Raman spectrometers has seen renewed interest in the area of Raman spectrometry. This new generation of spectrometers employs fiber-optic probes, holographic notch filters for rejection of the Rayleigh line, a single grating monochromator, and a charge-coupled device (CCD) detector for multichannel detection. These spectrometers contain a minimum of optical components as compared to conventional Raman instrumentation resulting in a high data throughput; and, once coupled to a laser and spectrometer, optical-fiber probes require no further alignment.
Despite the advantages of Raman spectroscopy over other spectroscopic techniques and the technological advances in the area of Raman spectrometry, Raman spectroscopy is, inherently, an insensitive technique. To achieve detection limits in the low ppm range would require either the use of a multiple pass cell or long acquisition times. In the 1970s, it was discovered that Raman scattering from molecules adsorbed on such noble metals as silver, copper, and gold can be enhanced by as much as 106 to 107. This phenomenon, called surface enhanced Raman spectroscopy (SERS), is still not understood despite intensive theoretical and experimental research. It is believed that more than one mechanism is involved in the SERS phenomenon. Initially, the SERS technique was used as a means to probe adsorption at metal interfaces both in electrochemical and gas-phase environments. This technique has proven useful in deducing the effects of interfacial structure and reactivity on the adsorption process. However, the sensitivity of the technique as well as its exceptional spectral selectivity has made SERS attractive for a broad range of analytical applications. SERS can be used for trace organic analysis and as a detection method in gas chromatography, liquid chromatography, and thin layer chromatography. Electrochemical SERS and SERS of chemically modified surfaces have been used to detect aromatic compounds and chlorinated hydrocarbons, organic contaminants of environmental concern, in the ppm concentration range.
There are many applications in which detection ofparticular chemical species or analytes is desirable, as for example, hydrocarbons that may be present in ground water, toxic vapors in industrial environments, explosives, metal ions, narcotics, toxic anions, and chemical warfare agents.
SERS is a very sensitive technique, but requires intimate contact between the SERS active surface and the analyte. This, in turn, requires that the sample be brought inside a chamber for analysis. However, there are practical problems in performing a SERS analysis that include: a) getting the sample inside a chamber; and b) purging the sample from the chamber. Therefore, a need exists for a system that overcomes the above-referenced problems.